Anna Maria Raspolli Galletti

• University of Pisa

Alkyl levulinates (ALs) are strategic compounds for the development of sustainable energy transition. In this regard, the direct alcoholysis of fructose and inulin for the selective ethyl levulinate (EL) production was investigated with a One‐Factor‐At‐a‐Time (OFAT) approach employing diluted H2SO4 as catalyst to clarify the role of the main reacti...

Diphenolic acid, or 4,4-bis(4-hydroxyphenyl)pentanoic acid, represents one of the potentially most interesting bio-products obtainable from the levulinic acid supply-chain. It represents a valuable candidate for the replacement of bisphenol A, which is strongly questioned for its toxicological issues. Diphenolic acid synthesis involves the condensa...

The production of oxygenated bio-additives for traditional fuels represents a key challenge due to their depletion in the near-future and their positive contribution to the reduction in environmental pollution. The present study considers the synthesis of 1-hexanol/hexyl hexanoate mixtures, two oxygenated Diesel bio-additives produced through the h...

The production of oxygenated bio-additives for traditional fuels represents a key challenge due to the depletion of fossil fuels in the next future and their contribution to environmental pollu-tion. In this context, the present study considers the synthesis of different mixtures of 1-hexanol/hexyl hexanoate produced through the catalytic hydrogena...

This work is focused on the application of Life Cycle Assessment (LCA) methodology for the quantification of the potential environmental impacts associated with the obtain- ment of levulinic acid from residual Cynara cardunculus L. biomass and its subsequent valorization in innovative bioplasticizers for tuning the properties as well as the process...

Levulinic acid production by acid-catalyzed hydrothermal conversion of (ligno)cellulosic biomass generates significant amounts of carbonaceous hydrochar, which is currently considered a final waste. In this work, the hydrochar recovered after the levulinic acid production, was subjected to cascade pyrolysis and chemical activation treatments (by H3...

Arundo donax L samples, before or after aqueous extraction to remove extractives, were subjected to chemical fractionation in H2SO4-catalyzed mixtures of 1-butanol and water. The partial miscibility of 1-butanol and water at room temperature allowed the separation of the three major feedstock components in separate streams (lignin, accumulated in t...

Starting from bioethanol it is possible, by using an appropriate catalyst, to produce ethyl acetate in a single reaction step and pure hydrogen as a by-product. Two molecules of hydrogen can be obtained for each molecule of ethyl acetate produced. The mentioned reaction is reversible, therefore, it is possible to hydrogenate ethyl acetate to reobta...

In this work, a three-step approach to isolate the main components of lignocellulosic cardoon, lignin and cellulose, was investigated. The raw defatted biomass, Cynara cardunculus, after steam explosion was subjected to a mild organosolv treatment to extract soluble lignin (L1). Then, enzymatic hydrolysis was performed to achieve decomposition of t...

The transition from fossil resources to renewable ones represents a pressing need. The acidogenic fermentation of biomass-derived ethanol to carboxylic acids represents a novel and smart possibility, opening the way for the production of further value-added bio-products through cascade chemical approaches. In this work, the hydrogenation of commerc...

Pollution associated to marine plastic litter is raising increasing concerns due to its potential harmful effects on human health, biota, and coastal ecosystems. However, limited information is available on the degradation behavior of plastics, especially biodegradable ones, in dune habitats. Moreover, the effects of plastics on dune plant growth a...

Commercial niobium and synthesized zirconium phosphates were tested as water-tolerant heterogeneous acid catalysts in the hydrothermal conversion of different bio-based substrates. Different acid-catalyzed reactions were performed using biomass-derived model compounds and more complex real lignocellulosic biomasses as the substrate. The conversion...

The cover feature image represents the role of carbon dioxide in the proposed biorefinery scheme based on CO2 capture by lignocellulosic biomass and the use of supercritical CO2 for the efficient pretreatment of giant reed under sustainable reaction conditions. The synergistic combination of supercritical CO2, FeCl3 and surfactant PEG400 allowed to...

Hydrothermal carbonization (HTC) is emerging as a promising technology for the management of sewage sludge. The fate of phytosanitary products, Polycyclic aromatic hydrocarbons (PAHs) and PCBs (Polychlorinated biphenyls) after HTC, as well as the formation of dioxins and furans, is still unclear. Moreover, only little information is available on th...

The depletion of fossil resources is driving the research towards alternative renewable ones. Under this perspective, 5‐hydroxymethylfurfural (HMF) represents a key molecule deriving from biomass characterized by remarkable potential as platform chemical. In this work, for the first time, the hydrogenation of HMF in ethanol was selectively addresse...

Cutaneotrichosporon oleaginosus is an oleaginous yeast with several favourable qualities: It is fast growing, accumulates high amounts of lipids and has a very broad substrate spectrum. Its resistance to hydrolysis by-products makes it a promising biocatalyst for custom tailored microbial oils. C. oleaginosus can accumulate up to 60 wt.% of its bio...

Hydrolysis and butanolysis of lignocellulosic biomass are efficient routes to produce two valuable bio-based platform chemicals, levulinic acid and n-butyl levulinate, which find increasing applications in the field of biofuels and for the synthesis of intermediates for chemical and pharmaceutical industries, food additives, surfactants, solvents a...

In recent years, biofuels have been attracting more attention, especially in Europe, due to the new regulations concerning the improvement of renewables in fuel composition. The acid-catalysed alcoholysis reaction of the cellulosic fraction of raw and pre-treated lignocellulosic biomasses, using n-Butanol (n-BuOH) and diluted inorganic acid as homo...

5-hydroxymethylfurfural (HMF), accessible from various feedstocks, represents an important renewable platform-chemical, precursor for valuable biofuels and bio-based chemicals. In this work, the continuous hydrogenation of an aqueous solution of HMF to give strategic monomers, 2,5-bis(hydroxymethyl)furan(BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofu...

p>In order to improve the lignin exploitation to added-value bioproducts, a mild chemical conversion route based on electrochemistry was investigated. For the first time, soda lignin Protobind™ 1000 (technical lignin from the pulp & paper industry) was studied by cyclic voltammetry to preliminarily investigate the effect of the main reaction parame...

Recent legislation concerning air pollutant emissions from ships (Tier III) has considerably decreased NOx emission limits for recreational ships with less than 500 gross tonnages and greater than 24 m load line length (LLL), the so-called “large yachts”. For these yachts, which adopt multiple Diesel engines with maximum power ranging from 800 to 2...

Giant reed (Arundo donax L.) is a promising source of carbohydrates that can be converted into single cell oil (SCO) by oleaginous yeasts. Microbial conversion of both hemicellulose and cellulose fractions represents the key step for increasing the economic sustainability for SCO production. Lipomyces starkeyi DSM 70296 was cultivated in two xylose...

Alkyl levulinates (ALs) represent outstanding bio-fuels and strategic bio-products within the context of the marketing of levulinic acid derivatives. However, their synthesis by acid-catalyzed esterification of pure levulinic acid, or by acid-catalyzed alcoholysis of furfuryl alcohol, although relatively simple, is still economically disadvantageou...

Nowadays, the solvothermal conversion of biomass has reached a good level of development, and now it is necessary to improve the process intensification, in order to boost its further growth on the industrial scale. Otherwise, most of these processes would be limited to the pilot scale or, even worse, to exclusive academic investigations, intended...

Hydrothermal carbonization of sewage sludge was carried out with the aim to evaluate the influence of process severity and initial solid content. Response surface methodology was applied to model yield and C yield responses. Enhanced dewaterability performance was recorded at mild processing conditions. The treatment promoted concentration and immo...

Single cell oil (SCO) represents an outstanding alternative to both fossil sources and vegetable oils from food crops waste. In this work, an innovative two-step process for the conversion of cellulosic paper mill waste into SCO was proposed and optimised. Hydrolysates containing glucose and xylose were produced by enzymatic hydrolysis of the untre...

Since safety hazards can occur during the life of a Li-ion battery, understanding its behavior under abusive conditions is important for the development of a safe cell. In this work, overcharge tests on commercial Li-polymer cells were conducted in a climatic chamber, resulting in gas evolution. A comprehensive post-mortem analysis of the abused ce...

A two-step exploitation of the giant reed cellulose to glucose and levulinic acid, after the complete removal of the hemicellulose fraction, was investigated using FeCl3 as catalyst. In the first step, the microwave-assisted hydrolysis of cellulose to glucose was optimised by response surface methodology analysis, considering the effect of temperat...

Hydrothermal carbonization offers the opportunity to reduce the issues related to the management of sewage sludge, enhancing dewaterability and avoiding thermal treatment prior landfill disposal or incineration, as water acts as a subcritical medium which catalyzes the process. The hydrochar obtained can find sustainable application as fuel, sorben...

The present investigation represents a concrete example of complete valorization of Eucalyptus nitens biomass, in the framework of the circular economy. Autohydrolyzed-delignified Eucalyptus nitens was employed as a cheap cellulose-rich feedstock in the direct alcoholysis to n-butyl levulinate, adopting n-butanol as green reagent/reaction medium, v...

Lignocellulosic biomass represents one of the most important feedstocks for future biorefineries, being a precursor of valuable bio-products, obtainable through both chemical and biological conversion routes. Lignocellulosic biomass has a complex matrix, which requires the careful development of multi-step approaches for its complete exploitation t...

In the recent years the progressive decrease in fossil petroleum resources and gradual deprivation of the environment have attracted increasing interest towards the use of biomass as renewable carbon source for the production of chemicals and transportation fuels. In particular, lignocellulosic biomass represents an abundant and inexpensive renewab...

Following the “Letter to the Editor regarding the article “Evaluation of the phytotoxicity of conventional and biodegradable plastic bags using seed germination tests” by Balestri et al. (2019) published on Ecological Indicators 102(2019):569–580” by Degli-Innocenti et al. (2019), we replied to the concerns expressed by Degli Innocenti and co-autho...

Hydrothermal carbonization (HTC) may be considered a promising process for the conversion of sewage sludge into valuable products such as fuel, sorbent materials or amendment. In this study the optimization of HTC of sewage sludge from urban wastewater treatment was conducted by using the Response Surface Methodology (RSM) approach for studying the...

The present work aimed to investigate and optimize the selective exploitation of hemicellulose and cellulose fractions of the energy crop Arundo donax L. (giant reed), to give xylose and levulinic acid, respectively. In order to improve the sustainability of this process, a microwave-assisted hydrolysis in the presence of FeCl3 was implemented usin...

Lignocellulosic biomass conversion to sugars represents the basis of future biorefineries, because sugars can be converted to valuable products through chemical or fermentative routes. In order to guarantee a sustainable bio-based economy, a multi-stage fractionation/conversion of biomass feedstock should be developed, in this way maximizing sugars...

In recent years, the replacement of fossil resources with renewable ones has received great interest, especially as regards the production of new valuable bio-products and bio-fuels, in order to replace the traditional petroleum-based ones. In this context, the exploitation of waste biomasses into added-value bio-chemicals is strongly encouraged. A...

Hydrothermal carbonization (HTC) of sewage sludge reduces the waste volume and can be source of energy and valuable products. Furthermore, HTC offers several advantages over conventional dry-thermal pre-treatments, as no prior drying is requested, and the high quality of the char produced promotes applications as energy production and storage, wast...

5-hydroxymethylfurfural (HMF) is one of the most important renewable platform-chemicals, a very valuable precursor for the synthesis of bio-fuels and bio-products. In this work, the hydrogenation of HMF to two furan diols, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), both promising renewable monomers, was i...

5-hydroxymethyl-2-furaldehyde is one of the top 12 bio-based chemicals, precursor of renewable monomers and biofuels. This key molecule can be obtained from the dehydration of monosaccharides and polysaccharides. In this work, the synthesis of HMF from fructose and inulin was investigated in the presence of a wide range of metal salts adopting a tr...

A large fraction of plastic litter found in natural environments is constituted by conventional not biodegradable plastic bags, and their adverse effects via ingestion or entanglement on terrestrial and marine organisms are largely documented. Biodegradable and compostable shoppers have been recently developed as alternative to traditional ones. Th...

Improvement of processes starting from renewable feedstocks to produce chemicals and biofuels up to now derived from fossil carbon feedstocks is paramount to creating environmentally sustainable industrial processes. Guerbet condensation of ethanol to give n-butanol represents a turning point not only respect to the traditional petrochemical “oxo”...

The ruthenium compounds [(η6-p-cymene)RuCl(κ2N-(HCNR)2)]NO3 (R = 4-C6H4Me, [1]NO3; 4-C6H4OH, [2]NO3; C6H11 = Cy, [3]NO3; 4-C6H10OH, [4]NO3; tBu, [5]NO3) were prepared in high yields from [(p-cymene)RuCl2]2, AgNO3 and the appropriate α-diimine. Compounds [2]PF6 and [4]PF6 were obtained by straightforward reaction of [(η6-p-cymene)RuCl(MeCN)0.66]PF6,...

A cascade strategy for the catalytic valorization of aqueous solutions of levulinic acid as well as of γ-valerolactone to 2-methyltetrahydrofuran or to monoalcohols, 2-butanol and 2-pentanol, has been studied and optimized. Only commercial catalytic systems have been employed, adopting sustainable reaction conditions. For the first time, the combin...

Nowadays, the transformation of lignocellulosic biomass into added-value products such as reducing sugars is attracting great attention. Pentose and hexose sugars are very important industrial intermediates because they represent a versatile platform for the synthesis of several valuable compounds through chemical or biotechnological approaches. Th...

In recent years, the replacement of fossil resources with renewable ones has focused great interest, expecially as regards the production of new valuable bio-products and bio-fuels, in progressive replacement of the traditional petroleum-based ones.The Waste Management Policy strongly encourages the valorization of waste biomasses into added-value...

Levulinic acid is a platform chemical obtained from acid-catalyzed hydrothermal conversion of cellulose-rich biomass. The low amounts of solid biomass which can be handled in the reactor limit the levulinic acid concentration in the aqueous stream, making the economic viability of the aqueous phase process unsuitable for large scale applications. N...

Eucalyptus globulus wood samples were subjected to preliminary aqueous processing to remove water-soluble extractives and hemicelluloses, and the resulting solid (mainly made up of cellulose and lignin) was employed as a substrate for converting the cellulosic fraction into mixtures of levulinic and formic acid through a sulfuric acid-catalyzed rea...

Furfural was produced in biphasic media using a microwave-heated reactor. Diverse substrates were considered: xylose (considered as a reference compound) or hemicellulosic saccharides from Eucalyptus globulus wood or corncobs. Operation was carried out at 170°C for the desired reaction time in the presence of an acidic catalyst (sulfuric acid or HC...

Up to now, on the industrial scale, the acid-catalysed hydrothermal conversion of lignocellulosic biomass has been targeted to the production of levulinic acid (LA), while the lignin fate has been neglected, and its use has been limited at most to the energy recovery. Now, an integrated investigation of the hydrothermal process for the synthesis of...

5-hydroxymethyl-2-furaldehyde (HMF) can be obtained from the hexose fraction of lignocellulosic biomass and its catalytic exploitation represents a big challenge for sustainability. Environmentally friendly oxidation of aqueous HMF to give 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA) was now studied through he...

We successfully prepared copper-based magnetic catalysts combining copper oxide and magnetite nanoparticles. These systems are active and selective in the oxidative homocoupling reaction of phenylacetylene in the absence of an external base. These systems are particularly interesting since the addition of an external base induces copper leaching by...

For the first time, the exploitation of hazelnut shells for the combined production of levulinic acid (LA) and hydrochar was investigated. The optimization of the catalytic hydrothermal treatment was performed both in autoclave and microwave reactor, approaching a maximum LA yield of∼9-12 wt%. Hydrochars recovered with high yield (∼43-47 wt%) were...

The chemical characterization of shell and cuticle from Tonda Gentile Romana hazelnut was carried out using analytical pyrolysis in the presence of hexamethyldisilazane followed by gas chromatography-mass spectrometry analysis (Py(HMDS)-GC/MS) and high-performance liquid chromatography with diode-array detection (HPLC-DAD). The aim was to acquire a...

Flexible polyurethane foams were prepared from solid waste residue derived from the hydrothermal acid treatment of the Arundo donax L. herbaceous biomass, which produced a very high yield of levulinic acid. An innovative, sustainable, and green liquefaction route was adopted to produce lignin-based flexible polyurethane foams by partially replacing...

5-Hydroxymethyl-2-furaldehyde (HMF) is a biomass-derived intermediate for the sustainable production of monomers and biofuels. However, most of its syntheses are performed under not environmentally and/or economically green conditions. In this work, the dehydration of fructose/inulin to HMF was optimized, employing aqueous medium, high substrate co...

5-hydroxymethyl-2-furaldehyde (HMF) is a key bio-based platform for the production of renewable monomers and bio-fuels. However, most of its syntheses are carried out under not sustainable conditions. In this work, the production of HMF from fructose and inulin was investigated following the Green Chemistry principles, adopting aqueous medium, appr...

Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance and environmentally benign nature. The LA transition from nich...

The removal of polychlorinated biphenyls (PCBs) both from siloxane transformer oil and hydrocarbon engine oil was investigated through the application of microwave (MW) irradiation and a reaction system based on polyethyleneglycol (PEG) and potassium hydroxide. The influence of the main reaction parameters (MW irradiation time, molecular weight of...

Philip Davies opened the discussion of the introductory lecture by Avelino Corma: Themetal nanoparticles inside the zeolites are in a different environment from those outside. Is there any difference in their chemistry and their catalytic behaviour? Avelino Corma answered: We were not able to determine the differences in reactivity, other than the...

Recycled paper needs a lot of mechanical/chemical treatments for its re-use in the papermaking process. Some of these ones produce considerable rejected waste fractions, such as "screen rejects", which include both cellulose fibers and non-fibrous organic contaminants, or "stickies", these last representing a shortcoming both for the papermaking pr...

Pinus pinaster wood was fractionated by aqueous treatments to yield a solution containing hemicellulose-derived saccharides (mainly of polymeric or oligomeric nature) and a solid phase enriched in cellulose and lignin. The solution containing polymeric or oligomeric hemicellulosic saccharides was acidified with sulfuric acid (up to 4 wt%) and heate...

With the awareness of the need for optimal and sustainable use of natural resources, hydrothermal treatment of biomass and biomass waste for energy and resource recovery has received increasing attention. The hydrothermal carbonization (HTC) of a biomass is achieved using water as the reaction medium and applying mild temperatures (180–250 ° C) und...

Background: Autohydrolysis of lignocellulosic biomass in liquid hot water has been widely studied owing to its high efficiency and relatively low cost. In the perspective of industrial applications, continuous or semi-continuous processes are more interesting than batch systems. Moreover, microwave heating of pretreatment systems has been proposed...

The characterization of the solid residue coming from the acid hydrolysis of giant reed (Arundo Donax L.) herbaceous biomass was performed and compared with the characteristics of two commercial technical lignins, i.e. a soda and a sulphate (kraft) one, in order to ascertain their differences, and thus better address their successive possible appli...

[PdCl2(dppb)] is highly active in the catalytic CO-ethene copolymerization in H2O-H(CH2)nCOOH (n = 0, 1 or 2). The influence on the productivity, the limiting viscosity number and the average viscosity molecular weight MW¯v of the following reaction conditions is investigated: (i) solvent composition; (ii) temperature; (iii) CO and ethene partial p...

The hydrothermal conversion of giant reed (Arundo donax L.) to furfural (FA) and levulinic acid (LA) was investigated in the presence of dilute hydrochloric acid. FA and LA yields were improved by univariate optimization of the main reaction parameters: concentration of the acid catalyst, solid/liquid ratio of the reaction mixture, hydrolysis tempe...

The acid-catalysed ketalization between ethyl levulinate and two different alkyl 1,2-diols (ethylene glycol and 1,2-dodecanediol) was investigated using different acid catalysts, e.g. p-toluensolfonic acid, Amberlyst 70, zeolite H-ZSM-5 and niobium phosphate. Good activity and recyclability were achieved in the reaction with ethylene glycol catalyz...

Today, the sustainable growth of the chemical and energy industries has become an indispensable benchmark of our society and the current development of the industrial sector based on fossil resources must be replaced by an alternative one, linked to renewable resources. By 2030, 30 % of the chemicals and materials production in Europe will be bio-...

An inductive measurement method was adopted to analyze the magnetic properties of magnetite nanopowders and the possibility to prepare samples having the same geometry is discussed from a macroscopic point of view. The influence of the chemical composition on magnetic and morphological characteristics of the samples was investigated by several meas...

Few-layer graphene, carbon nanotubes, and N-doped carbon nanotubes have been used to support Ru and/or Fe3O4 nanoparticles. The materials were prepared by a new single-step sustainable method that involves: 1) a simple procedure, 2) the use of propanol as a solvent, 3) short reaction times, 4) an efficient and energy-saving heat source, and 5) the...

Abstract The surface acidic properties of niobium phosphate solid acidic catalyst (NbP) have been analyzed by FT IR spectroscopy before and after reactivity tests concerning the hydrolysis and dehydration to furfural of xylose, as model molecule, or of real corn stover hydrolysates. Nitriles adsorption over the fresh NbP catalyst evidences POH and...

This paper deals with the characterization of magnetic iron oxide nanoparticles. Pure magnetite (Fe3O4) and noble metal doped magnetite were synthesized following a new sustainable microwave-assisted method. Furthermore, an experimental analysis was carried out to investigate the chemical and magnetic properties of these new nanopowders. Morphologi...

La sostituzione delle materie prime fossili con quelle rinnovabili rappresenta una necessità sempre più stringente sia in ambito energetico sia della chimica degli intermedi e dei materiali. Si stima infatti che nel 2030 il 30 % della produzione di composti chimici sarà bio-based. La conversione catalitica dei rinnovabili è un argomento estremament...

The fractionation of the structural components of lignocellulosic biomass (cellulose, hemicelluloses, and lignin) and the separate utilization of the resulting fractions for specific purposes, according to the philosophy of biorefineries, enables the development of sustainable processes for biomass utilization. In this work, Pinus pinaster wood was...

A semiquantitative analysis by means of midinfrared FT-IR spectroscopy was tuned for the simultaneous determination of cellulose, hemicellulose, and lignin in industrial crops such as giant reed (Arundo donax L.) and switchgrass (Panicum virgatum L.). Ternary mixtures of pure cellulose, hemicellulose, and lignin were prepared and a direct correlati...

An organic-inorganic hybrid material, PK-SiO2 (PK = polyketone), was employed as support for Pd catalysts. Their synthesis was carried out by MW irradiation of an ethanol solution of Pd(OAc)2 in the presence of the support. The obtained systems were characterized by solid state NMR, SEM, TEM, ICP, XPS, BET, gas porosimetry and tested in two probe r...

Furfural was obtained from corn stover hemicelluloses by a microwave-assisted, green and heterogeneously catalyzed two-step cascade process as follows: first step, hydrothermal fractionation of corn stover hemicelluloses, and second step, hydrolysis/dehydration of soluble hemicellulosic sugars over niobium phosphate to yield furfural at moderate te...